Method for improving the high temperature gel stability of borated galactomannans

ABSTRACT

A complexor solution and method of use are shown for providing controlled delay and improved high temperature gel stability of borated fracturing fluids. A base fluid is first prepared by blending together an aqueous fluid and a hydratable polymer which is capable of gelling in the presence of borate ions. The complexor is prepared by mixing a cross-linking additive capable of furnishing borate ions in solution with a delay additive. The delay additive is effective, within a selected pH range, to chemically bond with both boric acid and the borate ions produced by the cross-linking additive to thereby limit the number of borate ions initially available in solution for subsequent cross-linking of the hydratable polysaccharide. In addition to providing more precise control of the delay time, the complexor provides a reserve of borate which provides improved gel stability at higher temperatures.

BACKGROUND OF THE INVENTION

1. Cross-reference to Related Applications

This application is a continuation-in-part of the copending application of Jeffrey C. Dawson entitled "Method And Composition For Delaying The Gellation Of Borated Galactomannans", filed Jan. 16, 1990, Ser. No. 07/465,903 now U.S. Pat. No. 5,082,579.

2. Field of the Invention

The present invention relates to methods and compositions useful as aqueous well fracturing fluids. It particularly relates to a novel liquid complexor used to obtain controlled delayed gellation of borated polysaccharides and improved gel stability at temperatures above about 200° F.

3. Description of the Prior Art

During hydraulic fracturing, a sand laden fluid is injected into a well bore under high pressure. Once the natural reservoir pressures are exceeded, the fracturing fluid initiates a fracture in the formation which generally continues to grow during pumping. The treatment design generally requires the fluid to reach maximum viscosity as it enters the fracture which affects the fracture length and width. This viscosity is normally obtained by the gellation of suitable polymers, such as a suitable polysaccharide. In recent years, gellation has been achieved by cross-linking these polymers with metal ions including aluminum, antimony, zirconium and titanium containing compounds including the so-called organotitanates See, for instance, U.S. Pat. No. 4,514,309, issued Apr. 30 ,1985, and assigned to the assignee of the present invention.

The viscous fracturing fluid being pumped usually encounters high shear in the pipe string during pumping from the surface to the fracture and after entering the fracture, flows at low shear. Recent investigations indicate that the high shear encountered in the pipe string causes extensive degradation of the cross-linked fracturing fluid. Also, high fluid viscosities cause excessive back or friction pressures, limiting the pumping rate, which also affects fracture geometry. These investigations have shown that by delaying the gellation for several minutes during most of the high shear, higher pump rates can be obtained and the fluid generally exhibits better stability.

Recently, guar and guar derivatives cross-linked with borate ions have again become popular. In alkaline water having a pH greater than about 7.8, cross-linking of the guar polymer is essentially instantaneous. This action is probably due to the fact that borates easily and readily esterify with 1,2-cissoidial dialcohols or polyhydric alcohols, such as those found on the guar polymer. This esterification is readily reversible, especially at the elevated temperatures found in the well bore, so that free borate ion is always available. As a result, the delay of borate ion cross-linking systems is difficult to achieve.

Also, for each cross-linking agent, there is a generally recognized maximum temperature where the cross-linker fails to give any increase in viscosity over that observed for the base gel. For boron cross-linked gels, this upper temperature limit is recognized in the prior art as being between about 150° F. to 200° F.

Certain of the prior art borated guar systems have employed either slow dissolving metal oxides which slowly increase the fluid alkalinity, which in turn promotes cross-linking, or have used calcium borate salts having poor water solubility, relying upon the slow dissolution of borate ions for delay. In both cases, the delay action was based primarily on the slow dissolution of a solid in the aqueous fracturing fluid, resulting in poor control of the delay time and ultimate viscosity of the fluid. U.S. Pat. No. 4,619,776, issued Oct. 28, 1986, to Mondshine, is typical of the prior art in teaching the use of a sparingly soluble borate to achieve some degree of control over the cross-linking reaction.

Mondshine also discusses the use of sparingly soluble borates to achieve some degree of enhanced thermal stability since a "reserve" of boron is available for cross-linking over an extended period of time. However, Mondshine's gel stability examples only extend to an upper temperature limit of 110° C. (230° F.) and Mondshine advises the incorporation of organometallic agents to enhance extreme temperature conditions above 135° C. (275° F.). The introduction of impurities which are present in the sparingly soluble ores of Mondshine can also serve to degrade the overall performance of the fracturing job.

In Applicant's previously cited copending application, Ser. No. 07/465,903, now U.S. Pat. No. 5,082,579, there is described a novel chemical mechanism for delaying the cross-linking reaction of a borated fracturing fluid in which the borate ions are chemically chelated to reduce their initial availability, thus delaying the speed of the cross- inking reaction.

The present invention is directed to the additional discovery that such a chemical chelating mechanism can be used to provide a reserve of borate ions which provides high temperature gel stability for aqueous fracturing fluids at temperatures not previously possible with borated galactomannans.

SUMMARY OF THE INVENTION

The cross-linking system of the invention utilizes a novel complexor solution which both controls the gellation rate of an aqueous fracturing fluid containing a hydrated polysaccharide polymer and provides improved gel stability at temperatures up to about 300° F. and above. The complexor solution comprises a cross-linking additive and a delay additive which controls the rate at which the cross-linking additive promotes gellation of the hydrated polymer, the control rate being a function of the pH of the complexor solution. The cross-linking additive is a material which supplies free borate ions in solution and the delay additive is a material which attempts to bind chemically to the borate ions in solution, whereby the hydrated polymer is forced to compete with the delay additive for the free borate ions. Preferably, the delay additive is selected from the group consisting of dialdehydes having about 1 to 4 carbon atoms, keto aldehydes having about 1 to 4 carbon atoms, hydroxyl aldehydes having about 1-4 carbon atoms, ortho substituted aromatic dialdehydes and ortho substituted aromatic hydroxyl aldehydes. The most preferred delay additive is glyoxal.

The cross-linking additive is present in a preselected amount to provide a quantity of borate ions which would be sufficient to normally over-crosslink a base fluid forming a poor quality gel without the presence of the delay additive. The delay additive serves to mask the presence of at least a portion of the borate ions at low temperature, thereby providing a reserve of borate ions for cross-linking the fluid at higher temperatures and providing improved gel stability.

In the method of the invention, a hydratable polymer capable of gelling in the presence of borate ions is blended with an aqueous fluid to form a base fluid and the polymer is allowed to hydrate. A complexor solution is formed for the base fluid by combining a cross-linking additive capable of furnishing borate ions in solution with a delay additive, to chemically bond with both boric acid and the free borate ions produced by the cross-linking additive to thereby limit the number of borate ions available in solution for initial cross-linking of the hydrated polymer. The pH of the complexor solution is adjusted in order to control the rate of the subsequent cross-linking of the hydratable polymer. By properly selecting the amounts of cross-linking additive and delay additive in the complexor solution, a reserve of borate ions is available which are sufficient to cross-link the polymer and to increase the thermal stability of the fracturing fluid at temperatures over 200° F.

Additional objects, features, and advantages will be apparent in the written description which follows.

DETAILED DESCRIPTION OF THE INVENTION

In order to practice the method of the present invention, an aqueous (water or brine) based fracturing fluid is first prepared by blending a hydratable polymer into the base fluid. Any suitable mixing apparatus may be used for this procedure. In the case of batch mixing, the hydratable polymer and aqueous fluid are blended for a period of time which is sufficient to form a hydrated sol. Once the hydration of the polymer is complete, a predetermined quantity of complexor solution is added to the base fluid sufficient to achieve a desired cross-linking reaction time and provide a reserve of borate ions available for cross-linking over a period of time at higher temperatures. The mixture is pumped into the well bore as the cross-linking reaction takes place.

It has been disclosed that the general upper temperature limit for boron cross-linked gels is within the range from about 65° C. to about 100° C. By "higher temperatures"0 is meant temperatures above about 100° C. (212° F.), at which temperatures desired viscosity increases are not achievable with traditional boron cross-linked fluids.

Propping agents are typically added to the base fluid prior to the addition of the complexor. Propping agents include, for instance, quartz sand grains, glass and ceramic beads, walnut shell fragments, aluminum pellets, nylon pellets, and the like. The propping agents are normally used in concentrations between about 1 to 8 pounds per gallon of fracturing fluid composition, but higher or lower concentrations can be used as required. The base fluid can also contain other conventional additives common to the well services industry such as surfactants, corrosion inhibitors, buffers, and the like.

The hydratable polymer useful in the present invention can be any of the hydratable polysaccharides familiar to those in the well service industry which is capable of gelling in the presence of borate ions to form a gelled base fluid. For instance, suitable hydratable polysaccharides are the galactomannan gums, glucomannan gums, guars, derived guars and cellulose derivatives. Specific examples are guar gum, guar gum derivatives, locust bean gum, karaya gum, carboxymethyl cellulose, carboxymethylhydroxyethyl cellulose, and hydroxyethyl cellulose. The preferred gelling agents are guar gum, hydroxypropyl guar, carboxymethylhydroxypropyl guar, and carboxymethylhydroxyethyl cellulose. A suitable synthetic polymer is polyvinyl alcohol. The most preferred hydratable polymers for the present invention are guar gum and hydroxypropyl guar.

The hydratable polymer is added to the aqueous base fluid in concentrations ranging from about 0.10% to 5.0% by weight of the aqueous fluid. The most preferred range for the present invention is about 0.24% to 0.72% by weight.

The complexor solution which is used to achieve high temperature gel stability comprises a cross-linking additive and a delay additive which controls the rate at which the cross-linking additive promotes gellation of the hydrated polymer, the control rate being a function of the pH of the complexor solution. The cross-linking additive can be any convenient source of borate ions, for instance the alkali metal and the alkaline earth metal borates boron monoxide and boric acid. A preferred cross-linking additive is sodium borate decahydrate. The cross-linking additive is present in a preselected amount to provide a quantity of borate ions or boric acid sufficient to normally degrade a base fluid without the presence of its companion delay additive. As will be described, the delay additive serves to mask the presence of at least a portion of the borate ions at low temperature, thereby providing a reserve of borate ions for cross-linking the fluid at higher temperatures and provide improved gel stability. For lower temperature applications, the sodium borate decahydrate is normally present from about 5 to 25% by weight, most preferably about 10 to 15% by weight of the complexor solution. For higher temperature applications, the sodium borate decahydrate content will normally be increased, as will be discussed.

The delay additive used in the complexor solution is a material which attempts to bind chemically to the borate ions produced by the cross-linking additive in solution, whereby the hydrated polymer is forced to compete with the delay additive for the borate ions. As will be explained, the effectiveness of the delay additive in chemically bonding to the borate ions in the complexor solution is pH dependent. Thus, unlike the prior art systems which utilized slow dissolving metal oxides or calcium borate salts having poor water solubility, the present complexor does not rely upon the slow dissolution of solids.

Preferably, the delay additive is selected from the group consisting of dialdehydes having about 1-4 carbon atoms, keto aldehydes having about 1-4 carbon atoms, hydroxy aldehydes having about 1 to 4 carbon atoms, ortho substituted aromatic dialdehydes and ortho substituted aromatic hydroxyl aldehydes. Preferred delay additives include, for instance, glyoxal, propane dialdehyde, 2-keto propanal, 1,4-butanedial, 2-keto butanal, 2,3-butadione, phthaldehyde, salicaldehyde, etc. The preferred delay additive is glyoxal due to its ready availability from a number of commercial sources. Preferably, the delay additive is present in the range from about 5 to 40% by weight, most preferably about 15 to 30% by weight of the complexor solution. The preferred ratio of glyoxal to sodium borate ranges from about 1:0.1 to 1:1 at lower temperatures, and can approach 1:0.05 at higher temperatures.

Glyoxal, a 1,2-dialdehyde, hydrates to form 1.1.2.2-tetrahydroxyethane which favorably binds to the borate ions provided by the cross-linking additive of the complexor. As the pH of the complexor solution increases, the rate of gellation declines. As the pH of the complexor solution decreases, the rate of gellation increases. Thus, by adjusting the pH of the complexor solution within a preselected range, extremely accurate control of the cross-linking delay time can be achieved. Experimental delay times have ranged from 10 to 300 seconds by varying the pH of the complexor solution from about 5.0 to 11.50, respectively.

The complexor can also contain a stabilizer which increases the shelf life of the complexor and can serve to enhance the delay time. Suitable stabilizers include, for instance, polyhedric alcohols such as pentaerythritol glycerin, lanolin, mono and oligosaccharides having multiple hydroxyl groups, and the like. The preferred stabilizer is sorbitol, a reduced sugar. The stabilizer is preferably present in the range from about 5 to 20% by weight, most preferably about 8 to 10% by weight of the complexor solution.

The complexor mixture is prepared by heating to a temperature ranging from ambient to 105° C. for 1 to 5 hours. Most preferably heating should range from 65°-80° C. for 2 to 4 hours.

The complexor of the invention can be used to control the delay time of a cross-linked fracturing fluid being pumped into a well bore traversing the subterranean formation to be fractured. The fracturing fluid is pumped at a rate sufficient to fracture the formation and to place propping agents into the fracture. A typical fracturing treatment would be conducted by hydrating a 0.24 to 0.72% galactomannan based polymer, such as a guar, in a 2% (wt/vol) KCl solution at a pH ranging from about 5.0 to 8.5. The pH of the complexor would be adjusted with caustic prior to the treatment to provide the desired delay time. During actual pumping, a buffer would be added to increase the hydrated polymer pH to above 8.0, followed by addition of the complexor, and typically a breaker and proppant. The complexor is preferably added in the range from about 1 to 20 gallons per thousand gallons of fracturing fluid, most preferably in the range from about 2 to 8 gallons per thousand gallons of fracturing fluid. During the treatment, the area close to the well bore will typically begin cooling gradually, resulting in a decreasing gellation rate. The delay time can be easily readjusted to accommodate the cooling by acidifying the complexor.

The following examples of the cross-linked fracturing fluid of the present invention illustrate the controlled delay which can be achieved at lower temperatures and the improved gel stability which can be achieved at higher temperatures. Included are examples of glyoxal/borate formulation, data relating gellation times to complexor pH and gellation stability after cross-linking.

EXAMPLE 1 Complexor Preparation

Into 300 parts of 40% aqueous glyoxal are added, with stirring, 130 parts of sodium borate decahydrate yielding a milky white suspension. Then, 65 parts of 25% aqueous yellow solution. The solution pH can range from 4.90 to 6.50. Afterward, 71.4 parts of 70% aqueous sorbitol are added to the solution followed by heating to 95° C. for 3 hours. During heating, the solution color changes from pale yellow to amber. After cooling to ambient, the solution pH ranges between 4.50 and 5.00. Each gallon of complexor contains a boron concentration equivalent to 0.29 pounds of elemental boron or 1.65 pounds of boric acid.

EXAMPLE 2 Gellation Rate

The base sol used to determine the gellation rate is prepared by adding, with vigorous stirring, 2.4 parts of a 0.4 D.S. hydroxypropyl guar gum and 0.18 parts of sodium bicarbonate to 500 parts of 2% aqueous potassium chloride solution. After the addition, the stirring rate is reduced to provide mild agitation to the sol for 2 hr. Then, 3.2 parts of 30% aqueous potassium carbonate are added which buffers the sol to about pH 10.0.

Meanwhile, the complexor prepared in Example 1 is blended with 0,4,8 and 12 parts of 25% aq sodium hydroxide per 100 parts of complexor. The pHs of the treated complexors are shown in Table 1.

Then, 250 parts of hydrated sol are transferred to a one liter Waring blender jar and sheared at a rate sufficient to create a vortex exposing the hub nut on the blender blades. Next, 0.98 parts of the treated complexors are added to the sol vortex. The time required for the fluid to viscosify and cover the hub nut is defined as the vortex closure time. These data are also shown in Table 1.

                  TABLE 1                                                          ______________________________________                                         Parts of 25% aq NaOH                                                                            Vortex Closure                                                                             Complexor                                         per 100 parts complexor                                                                         Time (sec.) pH                                                ______________________________________                                         0                 22         4.92                                              4                 44         5.80                                              8                121         6.09                                              12               275         8.28                                              ______________________________________                                    

EXAMPLE 3

Shear and thermal stability of borated galactomannans:

The preparation of the base sol used in this example is mixed as described in Example 2. After hydrating for 2 hours, the 500 parts of base sol are treated with 4.5 parts of 30% aqueous potassium carbonate which buffers the sol to about pH 10.3. Afterward, 2.28 parts of complexor containing 0.17 parts of 25% aqueous sodium hydroxide are added to the vigorously stirring sol. After 100 seconds, 42 parts of gel are syringed into a Fann 50C cup. The sample is sheared at 102 sec⁻¹, using an R1B1 cup and bob combination, while heating to 190° F. in a preset bath and pressuring to 110 psi with nitrogen. The sample is heated and sheared for 20 minutes followed by a rate sweep using 170, 128, 85 and 42 sec⁻¹, while recording stress. These sweeps are repeated about every 30 minutes and the interim rate between sweeps is 102 sec⁻¹. After 359 minutes, the shearing is stopped while heating continues overnight. A final sweep is made after 22 hours and 21 minutes. The rates and stresses are used to calculate the Power Law indices, n' and K' described in the API bulletin RP-39. From the calculated indices, the viscosity of the gel at various shear rates can be calculated and are shown in Table 2 at 170 and 85 sec⁻¹ over time.

                  TABLE 2                                                          ______________________________________                                         Time    Temp              K       Viscosity (cp) at                            (min)   °F.                                                                               n'      lb.sub.m /ft.sub.2                                                                     170 s.sup.-1                                                                          85 s.sup.-1                           ______________________________________                                          20     183       0.7005  0.0497  512    630                                    51     191       0.7090  0.0420  451    552                                    81     191       0.6631  0.0456  387    489                                   112     192       0.8411  0.0144  306    341                                   141     192       1.0762  0.0040  286    271                                   172     190       1.1220  0.0028  252    231                                   202     191       1.1981  0.0016  210    183                                   232     191       1.1293  0.0020  185    169                                   262     192       1.1020  0.0022  181    169                                   292     192       1.0589  0.0025  160    155                                   359     193       0.9811  0.0020   86     87                                   1341    192       0.5486  0.0034   16     20                                   ______________________________________                                    

EXAMPLE 4

Shear and thermal stability of borated galactomannans:

The experiment in Example 3 is repeated using 4.0 parts 30% aqueous potassium carbonate and 1.62 parts of untreated complexor prepared in Example 1 . After 60 seconds, 42 parts of gel are syringed into the Fann 50C cup. The fluid is sheared at 102 sec⁻¹ while heating to 160° F. in a preset bath and pressuring to 110 psi with nitrogen. The rate sweeps are conducted as described in Example 3. After 233 minutes of heating and shearing, the shearing is stopped while heating overnight continues. A final sweep is made after heating for 19 hours and 40 minutes. These data are shown in Table 3.

                  TABLE 3                                                          ______________________________________                                         Time    Temp              K       Viscosity (cp) at                            (min)   °F.                                                                               n'      lb.sub.m /ft.sub.2                                                                     170 s.sup.-1                                                                          85 s.sup.-1                           ______________________________________                                          20     160       0.4708  0.1844  583    841                                    51     164       0.4824  0.1530  513    735                                    80     163       0.5501  0.1038  493    674                                   111     163       0.5143  0.1143  452    632                                   141     164       0.5275  0.1047  443    614                                   171     163       0.5224  0.1044  430    599                                   203     163       0.6097  0.0625  403    529                                   233     162       0.6572  0.0419  345    437                                   1180    163       0.7992  0.0011   19     21                                   ______________________________________                                    

EXAMPLE 5

Shear and thermal stability of borated galactomannans:

The polymer used in Examples 3 and 4 is a hydroxypropyl guar gum. The polymer used in this example is 3.0 parts of a nonderivatized guar gum in 500 parts of 2% aqueous potassium chloride solution mixed as described in Example 2. The sol is stirred for 2 hours prior to adding 4.5 parts of 30% aqueous potassium carbonate and 1.12 parts of triethanolamine, a temperature stabilizer. Then with vigorous stirring, 1.30 parts of untreated complexor prepared in Example 1 are added. After 60 seconds of shear, 42 parts of gel are syringed into a Fann 50C cup. The gel is then sheared at 102 sec⁻¹ while heating to 245° F. in a preset bath and pressuring to 110 psi with nitrogen. The rate sweeps are routinely made as described in Example 3. The final sweep is made after shearing and heating for 149 minutes. These data are shown in Table 4.

                  TABLE 4                                                          ______________________________________                                         Time    Temp              K       Viscosity (cp) at                            (min)   °F.                                                                               n'      lb.sub.m /ft.sub.2                                                                     170 s.sup.-1                                                                          85 s.sup.-1                           ______________________________________                                         20      239       0.4516  0.1763  505    738                                   50      244       0.7736  0.0298  446    521                                   83      245       1.1109  0.0046  389    360                                   119     245       1.3101  0.0008  194    157                                   149     245       1.3858  0.0003  102     78                                   ______________________________________                                    

The following example further illustrate the use of the complexor as a high temperature stabilizer. These examples describe three mixtures of the complexor (original) prepared in Example 1 and additional 40% aq glyoxal. The three mixtures are described as per gallon compositions in Table 5. COMPLEXOR A is a 1:1 volume ratio of original complexor and 40% aq glyoxal. COMPEXOR B is a 1:0.75 volume ratio of complexor to glyoxal and COMPLEXOR C is 1:0.5 volume ratio. In each case, the final COMPLEXOR A, B or C is treated with 25% (wt) caustic solution in a 1 (as complexor):0.2(as caustic) volume ratio.

                  TABLE 5                                                          ______________________________________                                         COMPLEXOR A                                                                    (Per Gallon)                                                                   0.416 gal original complexor from example 1                                    0.416 gal Glyoxal                                                              0.167 gal 25% NaOH                                                             COMPLEXOR B                                                                    (Per Gallon)                                                                   0.478 gal original complexor from example 1                                    0.357 gal Glyoxal                                                              0.167 gal 25% NaOH                                                             COMPLEXOR C                                                                    (Per Gallon)                                                                   0.555 gal original complexor from example 1                                    0.278 gal Glyoxal                                                              0.167 gal NaOH                                                                 ______________________________________                                    

The use of approximately using 6 gallons of COMPLEXOR B per thousand gallons of fracturing fluid has been shown to produce a stable gel at 250° F. Six gallons of COMPLEXOR B contains 2.86 gallons of original complexor from Example 1, 2.14 gallons of 40% aq glyoxal and 1 gpt 25% (wt) aq NaOH. At this concentration, the boron content is equivalent to 0.82 pounds of elemental boron or 4.72 pounds of boric acid.

COMPLEXOR C has been shown to provide more high temperature stability versus time. COMPLEXOR C is used at a concentration of 3 gallons per thousand gallons of aqueous fracturing fluid at 200° F. This concentration of COMPLEXOR C includes 1.725 gallons of original complexor, 0.861 gallons of glyoxal and 0.414 gallons of 25% NaOH. At this concentration, the boron equivalent is 0.49 pounds as elemental boron or 2.85 pounds as boric acid.

Tables 7 and 8 which follow illustrate two different cross-linker loadings and the effect on gel stability. Tables 9 and 10 show the difference in high temperature gel stability achieved by adding extra glyoxal. Tables 11 and 12 illustrate the results achieved with different concentrations of complexor.

                  TABLE 6                                                          ______________________________________                                         Fluid System: 0.6% (wt/vol) guar gum.                                          Additive: 6 gallons per thousand COMPLEXOR C.                                  Time  Temp             K      Viscosity (cp) at                                (min) °F.                                                                              n'      lb.sub.m /ft.sub.2                                                                    170 s.sup.-1                                                                         100 s.sup.-1                                                                          40 s.sup.-1                         ______________________________________                                          16   282      .687    22.3455                                                                               448   529    704                                  44   295      1.047    2.2667                                                                               289   281    270                                  73   296      .944     2.7715                                                                               208   214    225                                 101   296      .619     7.8682                                                                               111   136    193                                 129   296      .35     19.1562                                                                               68    96     174                                 158   296      .167    35.5508                                                                               49    77     165                                 186   296      .08     47.4719                                                                               42    69     159                                 214   296      .035    55.8269                                                                               39    66     159                                 243   296      .011    59.3442                                                                               37    62     155                                 271   295      .009    57.5   35    60     149                                 299   295      .008    55.6496                                                                               34    58     143                                 328   295      .008    53.5614                                                                               33    56     138                                 354   295      .009    51.1647                                                                               32    53     132                                 383   296      .014    50.1524                                                                               32    53     132                                 468   297      .003    51.3927                                                                               31    52     130                                 496   297      .017    49.1633                                                                               32    53     131                                 524   297      .009    52.1793                                                                               32    54     135                                 581   297      .005    53.0392                                                                               32    54     135                                 610   297      .006    52.2661                                                                               32    54     134                                 638   297      .014    50.7602                                                                               32    54     134                                 695   297      .026    47.1913                                                                               32    53     130                                 ______________________________________                                    

                  TABLE 7                                                          ______________________________________                                         Fluid System: 0.54% (wt/vol) guar gum.                                         Additive: 6.5 gallons per thousand gallons COMPLEXOR B.                        Time  Temp             K      Viscosity (cp) at                                (min) °F.                                                                              n'      lb.sub.m /ft.sub.2                                                                    170 s.sup.-1                                                                         100 s.sup.-1                                                                          40 s.sup.-1                         ______________________________________                                          2     81      .03     .2537   83   139    339                                 32    249       .627   .0758  535   652    917                                 62    251       .651   .0483  385   464    638                                 93    250       .846   .0155  337   366    421                                 122   249      1.029   .0058  325   320    312                                 152   249      1.177   .0024  288   262    223                                 182   248      1.347   .0009  281   234    170                                 ______________________________________                                    

                  TABLE 8                                                          ______________________________________                                         Fluid System: 0.54% (wt/vol) guar gum.                                         Additive: 6 gallons per thousand COMPLEXOR B.                                  Time  Temp             K      Viscosity (cp) at                                (min) °F.                                                                              n'      lb.sub.m /ft.sub.2                                                                    170 s.sup.-1                                                                         100 s.sup.-1                                                                          40 s.sup.-1                         ______________________________________                                          2     88      .134    .1554   87   138    305                                 32    236      .362    .2102  380   533    957                                 62    243      .533    .1068  465   596    914                                 92    248      .525    .0994  415   534    825                                 122   250      .64     .0515  388   470    654                                 152   253      .882    .0137  360   384    427                                 182   253      .992    .0076  349   351    354                                 ______________________________________                                    

                  TABLE 9                                                          ______________________________________                                         Fluid System: 0.36% (wt/vol) guar gum.                                         Additive: 2 gallons per thousand gallons COMPLEXOR C.                          Time  Temp             K      Viscosity (cp) at                                (min) °F.                                                                              n'      lb.sub.m /ft.sub.2                                                                    170 s.sup.-1                                                                         100 s.sup.-1                                                                          40 s.sup.-1                         ______________________________________                                          2    115      .014    1.2342 373   630    1556                                 32   190      .128    .7384  401   637    1417                                 63   194      .106    .6006  292   469    1063                                 93   196      .101    .5466  259   417    950                                 123   196      .109    .4436  219   351    794                                 153   197      .061    .478   184   303    717                                 183   198      .028    .5549  180   302    736                                 213   198      .015    .6023  183   309    762                                 244   199      .012    .6277  188   318    785                                 274   200      .009    .6471  191   323    801                                 304   200      .003    .6701  192   325    811                                 334   200      .001    .6747  191   325    811                                 364   200      .001    .6897  195   332    829                                 395   201      .002    .6767  193   327    816                                 455   201      .003    .6871  197   334    832                                 485   201      .002    .687   195   332    828                                 ______________________________________                                    

                  TABLE 10                                                         ______________________________________                                         Fluid System: 0.36% (wt/vol) guar gum.                                         Additive: 1.5 gallons per thousand gallons original                            complexor (Ex. 1).                                                             Time  Temp             K      Viscosity (cp) at                                (min) °F.                                                                              n'      lb.sub.m /ft.sub.2                                                                    170 s.sup.-1                                                                         100 s.sup.-1                                                                          85 s.sup.-1                         ______________________________________                                          33   194      .492    36.3312                                                                               267   350    380                                  63   191      .556    31.7173                                                                               324   410    441                                  94   192      .682    17.8267                                                                               348   412    434                                 125   193      .691    15.9739                                                                               327   385    405                                 148   194      .712    13.6233                                                                               310   362    379                                 178   198      .898     5.1232                                                                               303   320    326                                 208   199      1.036    2.5288                                                                               304   298    297                                 238   198      1.1     1.82   304   288    284                                 268   198      1.148    1.3111                                                                               280   259    253                                 298   198      1.27     .641  256   222    213                                 329   199      1.566    .1212 222   164    150                                 359   199      1.812    .0311 201   131    115                                 ______________________________________                                    

                  TABLE 11                                                         ______________________________________                                         Fluid System: 0.36% (wt/vol) guar gum.                                         Additive: 2.25 gallons per thousand gallons COMPLEXOR C.                       Time  Temp             K      Viscosity (cp) at                                (min) °F.                                                                              n'      lb.sub.m /ft.sub.2                                                                    170 s.sup.-1                                                                         100 s.sup.-1                                                                          85 s.sup.-1                         ______________________________________                                          3     80      .386    .0216   44    61     68                                  33   187      .514    .0684  270   350    378                                  64   192      .601    .0501  309   382    408                                  95   193      .594    .0517  308   382    408                                 121   193      .613    .0468  307   377    402                                 152   194      .684    .0332  314   372    391                                 183   193      .733    .0259  315   363    379                                 213   193      .781    .0199  310   348    361                                 244   194      .897    .011   312   329    335                                 275   193      1.147   .0031  322   298    291                                 ______________________________________                                    

                  TABLE 12                                                         ______________________________________                                         Fluid System: 0.36% (wt/vol) guar gum.                                         Additive: 3 gallons per thousand gallons COMPLEXOR C.                          Time  Temp             K      Viscosity (cp) at                                (min) °F.                                                                              n'      lb.sub.m /ft.sub.2                                                                    170 s.sup.-1                                                                         100 s.sup.-1                                                                          40 s.sup.-1                         ______________________________________                                          16   193      .41     .186   430   589    1011                                 47   194      .328    .1807  274   392    725                                  78   195      .496    .0985  354   463    735                                 109   193      .371    .1644  311   435    774                                 140   194      .382    .1492  299   415    731                                 170   195      .421    .1164  285   387    659                                 201   194      .46     .1003  300   400    655                                 232   194      .469    .0978  306   406    661                                 263   194      .461    .1043  314   417    684                                 ______________________________________                                    

                  TABLE 13                                                         ______________________________________                                         Fluid: 0.6% (wt/vol) guar gum.                                                 Additive: 6 gallons per thousand COMPLEXOR A.                                  Time  Temp             K      Viscosity (cp) at                                (min) °F.                                                                              n'      lb.sub.m /ft.sub.2                                                                    170 s.sup.-1                                                                         100 s.sup.-1                                                                          40 s.sup.-1                         ______________________________________                                          20   243      .3181   .3957  571   820    1532                                 38   251      .3619   .2814  508   713    1280                                 56   265      .3198   .3662  533   765    1426                                 85   267      .5028   .1801  671   873    1377                                 98   275      1.044   .0157  941   919    883                                 128   277      1.263   .0054  1000  870    684                                 158   289      1.35    .0017  479   397    288                                 208   290      1.3     .0011  249   212    161                                 243   290      1.073   .0022  151   145    136                                 273   289      .89     .0034   93    98    108                                 303   288      .6667   .0064   55    66     89                                 333   288      .6582   .0056   47    56     77                                 ______________________________________                                    

An invention has been shown with several advantages. The cross-linking system of the present invention provides an increase in viscosity in an aqueous well fracturing fluid and a stable gelled fluid even at temperatures well above 200° F. The delayed borate cross-linking of the hydrated polymer occurs without the use of suspended solids and does not require the presence of an organometallic adjunct cross-linker to achieve gel stability at temperatures above 200° F. Because the delay mechanism does not rely upon the dissolution of solids in solution, the delay time can be precisely adjusted. The chemical delay mechanism also provides a reserve of borate ions at higher temperatures to improve gel stability.

The complexor of the invention can also be used in a dual cross-link system. Thus, by mixing a traditional borate cross-linker such as boric acid or sodium borate with the complexor, a faster cross-linking time is observed. This effect can be used to enhance the early performance of the system at high temperatures by adding a small amount of either boric acid or sodium borate. This small amount of traditional cross-linker will give extra viscosity to the fluid as it is transporting sand through the tubing string from the well surface. The small increase in viscosity which is observed does not otherwise interfere with the desirable properties of the fluid.

While the invention has been described with respect to its preferred form, it is not thus limited but is susceptible to various changes and modifications without departing from the spirit thereof. 

What is claimed is:
 1. A method of fracturing a subterranean formation comprising the steps of:blending together an aqueous fluid and a hydratable polymer capable of gelling in the presence of borate ions, thereby forming a base fluid; allowing the polymer to hydrate to form a hydrated base fluid; forming a complexor solution for the base fluid by combining a cross-linking additive capable of furnishing borate ions in solution with a delay additive, the delay additive being effective to chemically bond with the borate ions produced by the cross-linking additive to thereby limit the number of borate ions available in solution for subsequent cross-linking of the base fluid; adding the complexor solution to the base fluid to cross-link the fluid; and chemically masking at least a portion of the borate ions at low temperature while simultaneously providing a reserve of borate ions for cross-linking the fluid at higher temperatures.
 2. The method of controlling the cross-linking reaction of an aqueous fracturing fluid of claim 1, wherein the hydratable polymer is selected from the group consisting of:guars and derivatized guars, locust bean gum, karaya gum, carboxymethyl cellulose, carboxymethylhydroxyethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol and mixtures thereof.
 3. The method of controlling the cross-linking reaction of an aqueous fracturing fluid of claim 2, wherein the cross-linking additive is selected from the group consisting of:alkali metal borates, alkaline earth metal borates, boric acid boron monoxide and mixtures thereof.
 4. The method of controlling the cross-linking reaction of an aqueous fracturing fluid of claim 3, wherein said delay additive is selected from the group consisting of:dialdehydes having about 2-4 carbon atoms, keto aldehydes having about 3-4 carbon atoms, hydroxyl aldehydes having 2-4 carbon atoms, ortho substituted aromatic dialdehydes and ortho substituted aromatic hydroxyl aldehydes.
 5. The method of controlling the cross-linking reaction of an aqueous fracturing fluid of claim 5, wherein the delay additive is glyoxal.
 6. A method of fracturing a subterranean formation having a downhole temperature above about 100° C. comprising the steps of:blending together an aqueous fluid and a hydratable polymer capable of gelling in the presence of borate ions, thereby forming a base fluid; allowing the polymer to hydrate to form a hydrated base fluid; providing a source of borate ions for cross-linking the base fluid at low temperatures; forming a complexor solution for the base fluid by combining a cross-linking additive capable of furnishing borate ions in solution with a delay additive, the delay additive being effective to chemically bond with the borate ions produced by the cross-linking additive to thereby limit the number of borate ions available in solution for subsequent cross-linking of the base fluid; adding the complexor solution to the base fluid to cross-link the fluid; and wherein the cross-linking additive is present in a preselected amount to provide a quantity of borate ions equivalent to at least about 2.50 pounds of boric acid per thousand gallons of base fluid, the delay additive serving to mask the presence of at least a portion of the borate ions at low temperature, thereby providing a reserve of borate ions for cross-linking the fluid at higher temperatures and providing improved gel stability. 